CZ109299A3 - Fadeless elastomeric polyurethane mouldings and process for producing thereof - Google Patents

Abstract

A process for the production of micro-cellular or non-cellular, light-stable elastomeric, flexible or semi-flexible polyurethane mouldings which are especially suited for window encapsulation applications from a reaction mixture by the reaction injection moulding process, wherein: A) an isocyanate component containing an isophorone diisocyanate (IPDI) trimer/monomer mixture having an NCO content of from 24.5 to 34 % by weight, is reacted with B) isocyanate-reactive components comprising: b1) a polyetherpolyol having terminal OH groups, an average nominal functionality of 2 to 4, and an average equivalent weight of from 800 to 4000; b2) at least one chain extender component having as functional groups only aliphatic or alicyclic OH groups; b3) at least one amine-initiator component; in the presence of C) at least one catalyst component selected from the group consisting of organolead (II), organobismuth (III), and organotin (IV) catalysts; D) at least one pigment component, and E) at least one antioxidant/UV absorber component.

Description

polyurethane lining sky‘a has caused their

Technical field

The present invention relates to microcellular or non-cellular, light-stable elastomeric, flexible or semiflexible polyurethane molds having a density of at least 900 kg / m ³ and a bending modulus according to ASTM D790 of between 5 and 300 MPa, and in particular between 10 and 120 MPa. of the reaction mixture by the reaction injection method (RIM) and a process for their preparation.

BACKGROUND OF THE INVENTION

The use of aliphatic or alicyclic isocyanates instead of aromatic isocyanates is known for the production of light-stable polyurethanes. Compared to aromatic isocyanates, however, aliphatic or alicyclic isocyanates have much less reactivity, which causes problems in obtaining a sufficiently short mold removal time (stripping). From a commercial point of view, the release times should preferably be less than 60 seconds.

Reducing the release time using appropriate catalytic systems has already been contemplated, for example, in US-A4,150,206 and U-A-4,2,9,411, more specifically for integral (whole) skin applications. The catalyst systems proposed in these US patents consisted essentially of a combination of a low molecular weight amine initiator with an organolead or optionally organovismuth catalyst. The proposed catalyst systems have been described with reference to a wide range of different solid skin foams or elastomers, and numerous examples have been given where the release time ranged from 1 to 6 minutes.

SUMMARY OF THE INVENTION

However, the present invention is directed to very specific light-stable polyurethane polymers, which are also particularly suitable for so-called window encapsulation applications, in which a flat gasket is pressed around the window periphery, especially the automotive window, to fit the window into the automobile frame. . These seals or other structures molded into windows must meet very stringent requirements in terms of light and heat stability, mechanical strength, softness and adhesion to the window and frame. Moreover, it is clear that the pressing process should allow a sufficiently short release time, preferably less than 60 seconds, to be economically feasible.

In the method of the present invention, an IPDI-based isocyanate component is used as it is more tolerant to use than e.g. HDI, from which the monomer fraction must first be stripped off as described in EP-A-0 690 085 with respect to its high volatility and its effects that strongly irritate the eyes. However, a significant disadvantage of IPDI is its reactivity, which is even lower than that of HDI. In this respect, EP-A-0 690 085 and U-A-5.5 0 2. 1 4 7 disclose the use of HDI instead of IPDI as isocyanates, as the use of IPDI in the aforementioned US Patent No. 4,772,639 generally requires peeling times of about 3 to 10 minutes, and in specific examples even 5 to 10 minutes, despite the use of organometallic Catalyst in combination with amine initiator and special HDI-based trimeric products and preferably IPDI.

According to the present invention, a novel process and a novel polyurethane elastomer have been found which make it possible, within an economically acceptable cycle time, to produce light-stable IPDI-based isocyanate-based elastomeric polyurethane moldings, which moldings are particularly suitable for window watering or encapsulation applications. .

The process according to the invention is characterized for this purpose more precisely by the composition of the various components of the polyurethane reaction mixture and the conditions under which the reaction injection molding process is carried out as defined in the appended claim 1.

In general, the process of the present invention is directed to the production of light-stable elastomeric polyurethane moldings according to the reaction injection molding (RIM) process, which moldings are suitable for encapsulating or potting windows, but which can also be used for other applications, e.g. cars (decorative moldings, fillings, linings) or other vehicles such as door panels, lids, etc., or even furniture. The obtained polyurethane moldings are non-cellular or microcell and have a density of at least 900 kg / m ³ . They are flexible or semi-flexible and have a flexural modulus according to ASTM D790 of between 5 and 300 MPa, typically between 10 and 120 MPa, and most typically between 10 and 70 MPa.

In the method of the present invention, the reaction mixture is injected under high pressure into a closed mold into which a slug, e.g. The reaction mixture comprises an IPDI based isocyanate component A, the reactive isocyanate component B, and at least one catalyst, at least one pigment and at least one antioxidant and a radiation absorber.

The isocyanate component A comprises an IPDI trimmer / monomer mixture having an NCO content of from 24.5 to 34, preferably from 26 to 32% by weight, and hence an average calculated functionality of from 2.2 to 2.7 and a calculated trimmer content of from 20% to 20%. up to 70 wt.%. These calculated values are based on the assumption that a purely moriomeric IPDI has a theoretical one.

NCO content of 37.8% and functionality 2, while pure trimeric IPDI has a theoretical NCO content of 18.9% and a theoretical functionality of 3, so that possible oligomers that may be present in the IPDI trimer are not taken into account in the above calculated values. It has been found that, in conjunction with the specific choice of the other components described below, a sufficiently short mold removal time and good light and heat stability for values above given lower limits can be obtained, while these values should remain below the given upper limits as otherwise, the mechanical strength would be lower (i.e., the polyurethane material would be more brittle), the material would be more rigid and the viscosity of the isocyanate component would be too high due to optimum processability and mixing of the components. The most preferred IPDI trimer is the isocyanurate derivative of IPDI.

In addition to the IPDI monomers and trimers, the isocyanate component may further comprise, as far as possible, up to 10 wt% of IPDI prepolymers with isocyanate reactive compounds containing 2 to 4 isocyanate-reactive hydrogen-containing groups, preferably hydroxyl groups. The addition of such prepolymers can improve glass adhesion properties.

With respect to the isocyanate component, it should be noted that this component may contain, in addition to the IPDI monomer / trimmer mixture, small amounts of other isocyanate monomers or polymers, in particular HDI trimers, especially in an amount less than 5 wt. % based on the weight of the isocyanate component.

The reactive components of isocyanates B comprise a polyether polyol component (b1), a chain extension component (b2) with only hydroxyl groups, in particular glycols, and an amine initiator t.

(b3), which forms a common catalytic system with the main catalytic system. · · · · · · · · * * * * * * * * * * * * The catalyst (s) (C) and which comprises crosslinking agents and / or chain extenders.

The polyether polyol component b1 contains only hydroxyl-terminated polyether polyols (OH). It should be noted that individual polyols or mixtures of polyols may be used. These have an average equivalent weight of from 800 to 4000, more preferably from 1000 to 2000, and a nominal average functionality of between 2 and 4. The primary OH content is generally comprised of 0 to 95% and more specifically 0 to 90%, excluding the first embodiment of the invention, polytetramethylene glycol. (PTMG) as polyether polyol. In fact, these PTMGs have a primary OH content of 100% and a nominal functionality of 2.

However, in a preferred embodiment of the process of the present invention, the polyether polyol component b1 is a propylene oxide (PO) and optionally ethylene oxide (EO) addition product on a low molecular weight polyol-alcohol initiator, wherein the amount of ethylene oxide, if present, is less than 30% of the total amount of ethylene oxide; propylene oxide.

The nominal functionality of the polyether polyol corresponds to that of the initiator used or the nominal functionality of the initiators used in the case of the polyol blend. In practice, the real functionality of a conventional polyether polyol is less than its nominal functionality, due to the fact that the proportion of propylene oxide (PO) used can be isomerise during the polymerization reaction, thus also forming unsaturated monools (functionality = 1). In the case of conventional alkali (KOH) catalysed polymerization reactions, the equivalent monool content may, for example, be up to 20% and typically between 5 and 20%, so that, for example, nominal functionality 2 and 3 corresponds to a typical real functionality of about 1.7, respectively. about 2.5. However, there is now a new one

I generation catalysed by DMC (double metal cyanide) catalyzed · · · ·

Polyether polyols having a significantly reduced monool content (less than 5% and typically between 0.5 and 3%), so that their real functionality is close to their nominal functionality.

Such polyether polyols are, for example, available from ARCO (ACCLAIM® series) and OLIN and are described, for example, in U-A-5,426.08 1; US-A5,470.8 1 3 and U S-A-5.4 9 8.5 8 3, which are incorporated by reference.

Polyether polyols with a low to zero content of primary OH groups which still provide a sufficient cure rate can be used according to the invention. In order to further reduce the curing time or to reduce mold removal in the case of conventional polyether polyols, it is preferable to use a polyether polyol having a primary OH group content of at least 70% and more preferably at least 80% and / or a basic polyether polyol prepolymerized with part of the isocyanate component. IPDI monomer to form a quazipolyol prepolymer (QPP) with terminal OH groups. In the case of QPP, the preferred primary hydroxyl content is at least 40% and even more preferred is at least 70%. The prepolymerization reaction to form the QPP is carried out in the presence of a suitable catalyst, such as organo-organo, organotin or organo-mismatch carboxylates, and / or at a higher temperature, eg at a temperature in the range of 20 to 100% depending on the amount of catalyst. The optimum final viscosity of such a QPP polyol is 1.5-10 times higher than the initial base polyol viscosity, while the viscosity of the final QPP polyol at 25 ° C should in any case be less than 10,000 mPas and rather than 6,000 mPas to ensure optimal mixing and the flow of the reactive PU mixture into the mold. First of all, the basic advantages of using QPP are that QPP increases reactivity, i.

• cure rate, reaction mixture (which is due to the higher equivalent).

0 0 • 000 00 • · initial molecular weight leading to a faster increase in the molecular weight of the reaction mixture) than isocyanate prepolymers with NCO-terminated groups (where reducing the NCO content reduces the number of exothermic reactions) and secondly that the viscosity of the polyol mixture is in particular, its physical stability is increased so that, in other words, less sedimentation, decantation or separation of the components in the mixture occurs when not mixed. In view of these advantages, a specific preference is given to the use of quasi-polyol hydroxyl-terminated prepolymers (QPPs) in the process of the present invention.

In the case of conventional polyether polyols, preference is given to reducing the required curing or mold removal time, an average nominal functionality of from 2.5 to 4 and an average equivalent weight of from 1000 to 1500, especially when the polyether polyol has a primary OH group content of less than 70%, or in the case of QPP-modified polyether polyols where the primary OH group content is less than 40%.

According to a preferred embodiment of the invention, it has been found that the curing or stripping time of molds can also be reduced by using polyether polyols having a low monool content, in particular an equivalent monool content, of less than 5%. As described hereinabove, such polyether polyols are available, e.g., from ARCO. These DCM-catalyzed polyether polyols not only have a low monool content, but in most cases also have a low to zero content of primary OH and EO. These polyether polyols with a low equivalent monool content are preferred in the process of the present invention not only in terms of higher reactivity but also in terms of additional mechanical strength and resistance to corrosion. This can be achieved by comparison with conventional polyether polyols with the same nominal functionality and hence with lower real functionality.

In the case of polyether polyols having a low monool content, an average nominal functionality of from 2 to 4, preferably from 2 to 3, for a minimum elastomer stiffness, and an average equivalent weight of from 1000 to 2000, in particular in the case where the polyether polyol has a primary OH content of less than 40%. Furthermore, the low monool polyether polyol can be prepolymerized just like conventional polyether polyols to a polyol quasi-prepolymer (QPP) having terminal hydroxyl groups.

An advantage of the above-described preferred embodiments in which a further reduction in cure time or mold release or mold removal can be achieved is also that they allow the use of fewer catalysts for a given mold removal time, resulting in improved elastomer properties. Furthermore, the use of polyether polyols or mixtures thereof having a low average primary hydroxyl group content, e.g. between 0 and 40%, and hence a low average EO content, more particularly less than 20% and preferably less than or equal to 10%, may be important. water and related characteristics of a given elastomer, since some of the primary hydroxyl groups in the polyether polyols arise from the ethylene oxide terminations (EO) and thus a minimum amount of EO is required to produce a certain amount of primary hydroxyl groups. In the case of polyether polyols with a low content of primary OH groups, the use of QPP and / or polyols containing a small proportion of monools is preferred in the method of the present invention in reducing the mold removal time. In this way it can · ♦ ·· · «» »· ···. . ··.

• «· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Λ ·······.

the amount of EO with respect to the sum of EO and PO can easily be less than 10% and may even contain 0% to maximize the reduction in water absorption and related shrinkage effects of the encapsulated PU elastomer.

Indeed, due to the reduction in water absorption, the amount of hydrophilic ethylene oxide units in a given polyether polyol is preferably less than 20% of the total amount of EO and PO, i.e. the sum of the number of EO and PO units, and most preferably less than or equal to 10%.

As mentioned hereinbefore, the polyether polyols used have a nominal functionality of from 2 to 4. In the case where conventional polyether polyols are used, the nominal functionality is preferably equal to about 3, while for the low monool polyether types the nominal functionality is preferably in the range of 2 to 4. 3. In combination with the above-mentioned characteristic of the poly-component, the desired softness, mechanical strength and resistance to light and heat (so-called WOM properties) can be obtained in this way and this is associated with a sufficiently short mold removal time ("stripping"). Furthermore, an average realistic functionality of at least 2 is preferred in reducing the water absorption of the elastomer or, in other words, avoiding the risk of the so-called "shrinkage" described herein, improving weather and heat stability and reducing mold removal time.

Finally, polyester polyols are not selected more than components b1 in the present invention, since in many cases it has been found that the unexplained effect of migration / incompatibility results in a greasy PU surface after aging or maturation.

Component b2, which has a chain extension effect, comprises chain extenders having only 1 as functional groups

hydroxyl (OH) groups, and especially aliphatic or alicyclic OH 9 999 9 99 9 9 9 9 9 9 9 9 9 9 9 9999 9 999 9 999 9

W9 99 * * · · 9 99 99 9 · 9 99 group, and is used in an amount of about 3 to 20 wt%, and more preferably about 5 to about 15 wt%, depending on the weight of components b1, b2 and b3. Due to the short mold removal time (" stripping ") combined with the required elastomer properties, i.e. softness, mechanical strength, etc., these chain extenders of the invention have a functionality of 2, an equivalent weight of up to 80 at most and a primary OH group content of at least 50. %.

Typical examples of b2 chain extenders having only OH groups as functional groups are; ethyleneglycol, propanediol (various isomers), butanediol (various isomers), pentanediol (various isomers), hexanediol (various isomers), diethylene glycol, 2-methyl-1,3-propanediol, 3-methyl-1, 1,5 - pentanedio 1,2,4-cyclohexanediol, neopentyl glycol and 1,4-cyclohexanedimethanol.

The amine initiator component b3 is used in an amount of about 2 to 10% by weight, preferably about 2.5 to 6% by weight, depending on the weight of the components b1, b2 and b3. Also, due to the required short demolding time and the required mechanical properties and hot stability of the polyurethane elastomer, the amine initiators according to this invention have

invention from two into three functional al ifatic NH-, nh ₂ - or ΟΗ- groups of which at least one is secondary n e b o primary amino, and equivalent weight up to 1 5 0 n and n, preferably up to 100 at most. These the compounds are so aliphatic

or alicyclic polyamines or alkanolamines.

The amino initiators are preferably selected from the following different compounds;

I. Crosslinking agents of the alkanolamine type with one secondary NH group and two OH groups, preferably a cross-linking NH group and two OH groups, preferably Primary OH-groups. Typical examples are diethanolamine (DEOA) and diisopropylamine, with DEOA being preferred.

II. Extenders with one primary NH ₂ group and one primary OH group located on adjacent carbon atoms. In these extenders, the reactivity of the primary NH ₂ group is reduced by the adjacent C-OH group, which is due to the steric hindrance and / or the effect of the oxygen atom in the adjacent OH group by electron withdrawal. This substantial part of this type of amine initiator can be represented as follows:

- C - C I

OH NH ₂

Typical examples are monoethanolamine (MEOA) and 2-amino-2-methyl (or ethyl) -1-propanol, with MEOA being preferred.

III. Extenders with one secondary NH group and one primary OH group. Typical examples are N-methyl (or ethyl) ethanolamine (= monomethyl (or ethyl) ethanolamine).

IV. Extenders with two primary NH ₂ groups, at least one of which is located on an alicyclic ring. A preferred example is isophorondiamine (IPDA).

V Extensions with two secondary NH groups having a branched alkyl or cycloalkyl group to which at least four carbon atoms are attached, or crosslinkers with three secondary NH groups of which at least two have a branched alkyl or cycloalkyl group to which they are additionally at least four carbon atoms attached. A branched alkyl or cycloalkyl group is, for example, isohexyl, tert-butyl, cyclohexyl, etc. Preferred examples are (1) R-NH NH-R (f; 2-MW: 285) ^CH 3 (2) R-NHNH-R ( f; 2-MW.228) (3) R-NH-X-NH-R-NH-R (1; 3-MW: 271) (4) R-NH-R-NH-R '(f: 2-MW: 256) (5) R-NH4-NH-R (1-2-MW: 170)

- the group R in examples (1) - (3) is isohexyl

- the group R 'in example (4) is CH

CH .CH

CH 2 CH 2 CH 2 CH

- the group R in example (5) is tert-butyl

Particularly preferred are amine initiators of Classes I, II and II

IN.

In order to achieve optimum mold removal time (de-molding), the amine initiator preferably comprises at least 1 wt% DEOA crosslinker based on the weights of components b1, b2 and b3 and, in view of increasing mechanical strength, preferably in conjunction with an amine initiator, especially MEOA. The functionality of the amine initiator between 2 and 3. Generally, a higher functionality results in a shorter mold removal time but also less mechanical strength, especially for soft elastomer types, and a lower functionality results in increased mechanical strength but a longer "stripping" time.

According to the invention, it has been found in this respect that, in particular, of softer types of polyurethane elastomers having a flexural modulus of less than the bending modulus. · · ··· ···

... ···· · · ···· ·· · ····

120 MPa, rather less than 70 MPa and in particular less than 30 MPa, good mechanical properties could be brought into line with a sufficiently short mold removal time for an average amine initiator (s) of between 2 and 3, unless used with DMC catalyzed polyols with a low monool content, in which case the functionality of the amine initiator can also be 3, which still allows good mechanical strength properties of the soft types of elastomers.

In view of the number of different amine initiators, it has further been found that in the case where the amine initiator contains 2 aliphatic primary NH ₂ groups, their amount must be less than 1.5 wt.% Based on the weight of components b1, b2 and b3; preferably less than 3 wt% when at least one primary NH ₂ group is attached to the alicyclic ring to prevent poor flow of the reaction mixture into the mold as well as a longer mold removal time.

In addition to the amine initiator described above, Catalyst System C of the present invention comprises at least one catalyst selected from the group consisting of organo-lead (II), organo-mismatch (III) and organotin (IV) catalysts, the latter catalyst in combination with said organo-lead and and / or in combination with a diazobicycloalkene catalyst.

Suitable organoaluminium and organo-mismatch catalysts are described in U.S. Pat. Nos. 4,150,206 and U.S. Pat. No. 4,292,411, the disclosures of which are incorporated herein by reference. The contemplated organolead and organovismuth catalysts are mainly lead (II) or bismuth (III) carboxylic acid salts.

• ·

0 0 0 • · ··· 0 0 0 0 0 0 0 0 0 0 ······· 0 0 0 0 0 0 0 000 000 0000000 0 0

00 00 00 00 00

According to the invention, the maximum concentration of the organometallic catalyst comprises 1.5 wt.%, More preferably 1 wt.%, And preferably 0.5 wt.% Based on the weight of components b1, b2 and b3 to reduce the risk of an undesirable metallic shiny appearance of the polyurethane elastomer surface. or maturing or storage in the case of dark colors. If the mold removal time is still too long, in addition to the amine initiators, other co-acting catalysts may be used, with diazobicycloalkene catalysts and / or said organotin catalysts being preferred among others, the combination of the latter being most preferred. of catalysts. Preferably, the diazobicycloalkene catalyst in an amount of 0.1-1 wt.%, And the organotin catalyst in an amount of 0.2-1 wt.%, Based on the weight of components b1, b2 and b3, are used in conjunction with the organolead catalyst. In order to compensate for the smaller amount of the catalyst by about 10% of the catalyst, the molding times can also be reduced by using the above-described quasi-polyol prepolymers, polyols containing a small amount of monool, or by adding an organovismic catalyst.

According to the invention, the maximum concentration of the organovismic catalyst comprises 1.5 wt% and most preferably at most 1 wt% based on the weight of components b1, b2 and b3. Indeed, higher amounts could cause problems with respect to the chemical stability of the polyol blend, since the organo-bismuth catalyst contains a certain amount of free acid, which could interfere with the eventual alkaline catalyst or amine initiator components in the polyol blend. The amount of free acid in the organo-bismuth catalyst comprises less than 60%, more preferably less than 25% and t

probably less than 10%.

• · · · · · · · · · · · · · · · · ·

As with the organolead catalyst, the removal times of the molds can be further reduced by the use of m quasi-polyol prepolymers, polyols containing small amounts of monools or other diazobicycloalkene or organotin catalysts in the above amounts, with the combination of organovismic catalyst with organotin catalyst being preferred. Further, an organo-bismuth catalyst with an organic catalyst can be used.

In the case where the organotin catalyst is used without an organolead or organovismic catalyst, the yoke contains a maximum concentration of 3% by weight based on the weight of components b1, b2 and b3. In this case, the organotin catalyst is used in combination with a diazobicycloalkene catalyst, more particularly in combination with 0.3 to 1 wt.%, Based on the weight of components b1, b2 and b3 of the latter catalyst.

The organotin catalysts are mainly either dialkyldistannoxane dicarboxylates corresponding to the general formula:

R OCOR 'OCOR' R

While R 1 is a (C 1 -C ₄ ) alkyl radical and R 'is a (C 1 -C ₁₂ ) branched or unbranched alkyl radical;

or tin (IV) carboxylates or dialkylcindialkoxides corresponding to the general formulas:

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

R,

0-R,

R.

.Sn .Sn

R.

STEED.

R.

OCR ii 2 O wherein R 1 is a (C 1 -C ₄ ) alkyl radical and R ₂ forms a (C 1 -C ₁₂ ) alkyl or naphthenic acid radical, wherein the alkyl radicals are linear or branched, with preference given to compounds in which R 1 is methyl and R ₂ is a (C 1 -C 4) alkyl or naphthenic acid radical, or also wherein R 1 is a butyl group and R ₂ is a (C 1 -C ₄ ) alkyl radical; or dialkylcíndichloridy wherein the Al alkyl group is a C i - C ₄ alkyl al ag group.

Most preferred are Sn (IV) carboxylates wherein R 1 is methyl and R ₂ is C 1 -C 11 alkyl.

Diazobicyclo-alkene catalysts are either diazobicycloalkenes as such or salts thereof with weak acids, including phenol, having a pKa value _higher than 4. They correspond to the formula:

N = C = N

U / where m = 3-7, n = 2-4.

Typically preferred is the 1,8-diazobicyclo (5.4.0) undecene-7 as well as the octoate or phenolate salts of the compound, with the phenolpha salt being most preferred.

Further, inorganic or organic pigments that are insoluble in the reaction mixture and which are typically dispersed in the isocyanate reaction compound are used in the process of the present invention. These are innate enough to be light and heat stable and are used at a concentration of 0.1510 wt% solids based on the weight of the reaction mixture and most likely at a minimum concentration of at least 0.3 wt% solids. Typical examples are carbon black, titanium dioxide, etc. The pigments used ensure the hiding power of the polyurethane material, so that it is no longer transparent, in other words, which is particularly important for the intended windows or interior trim moldings or automotive fillings.

In these latter applications, the polyurethane elastomeric materials must further be resistant to severe weather conditions including a combination of UV radiation, oxygen (ozone) and heat and must not lose or discolour under these conditions. Therefore, UV absorbers and antioxidants or anti-aging agents are used in the method of the present invention.

In particular, the antioxidants contain so-called primary oxidants, preferably:

0.1 wt.%, Preferably 0.2-0.6 wt.%, Based on the weight of the total reaction mixture, of the substituted phenolic type primary and non-oxidizing agents; and

0.1-1 wt.%, Preferably 0.2-0.6 wt.%, Based on the weight of the total reaction mixture, of substituted HALS (Hindered Aliphatic Light Stabilisers);

and optionally secondary antioxidants, namely:

0-5 wt.%, Most preferably less than 3 wt.% Based on the weight of the total reaction mixture, peroxide decomposers, preferably of the aliphatic or aromatic organophosphite type.

· · · · · · · · · · · · · · • · * ο * · * * * * * * * * * · · ·· · ····

The UV absorbers used are preferably of the benzotriazole type and are mainly used in an amount of 0.1-1 wt%, preferably 0.2-0.6 wt%, based on the weight of the reaction mixture.

If possible, other components such as;

water absorbers that are added to the isocyanate reactive compound to reduce the risk of small holes or dots such as zeolites, dry calcium oxide, etc .;

emulsifiers / flow regulators, inter alia to improve mixing and compatibility of the various components in the polyol blend and / or to improve the flow homogeneity of the reactive polyurethane blend into the mold;

internal release agents (molds) added to the polyol or possibly to the isocyanate compound, such as polydimethylsiloxano-polyether copolymers with free hydroxyl groups, metal salts of fatty acids (e.g. zinc stearate), and various fatty acid derivatives (fatty acid esters) acids, amides, ...) which allow to reduce the concentration and application frequency of the external release agent;

interior coatings for use on silane-type glass (including but not limited to also reactive silanes, ie silanes with active groups with respect to polyurethane elastomer), allowing to omit or reduce the amount of exterior glass coatings in encapsulation applications windows; and other additional components known per se for molding processes of polyurethanes.

· • · «« «• • • • ·

IQ ······· · ·

I- ⁷ · »· · · · ····

In the method of the present invention, the polyurethane reaction mixture described above is processed according to RIM technology, more specifically, two-component RIM technology with countercurrent mixing, wherein the isocyanate and polyol compound are supplied under high pressure to the mixing chamber from which the reaction mixture is injected into the closed mold. The polyol compound and the isocyanate compound are mixed according to the isocyanate index (NCO index) from 90 to 120, preferably from 95 to 110, and most preferably from 100 to 110. This form usually contains an already rigid or flexible molding, especially the perimeter of the window to be encapsulated with flexible or semi-flexible polyurethane gasket. In some applications, the entire surface of the insert may be coated with a polyurethane elastomer, for example in the case of smaller pieces to be mounted eg in the dashboard, or even larger pieces, such as the entire door panel. The thickness of the polyurethane elastomer typically ranges from 0.5 to 5 mm, and more typically from 1 to 4 mm.

The two main components or components of the reaction mixture, ie the isocyanate mixture and the polyol mixture, contain the various components described above. More particularly, the isocyanate composition comprises the component A, the organotin catalyst and, optionally, antioxidants, UV absorbers, interior release agents (molds), and glass primers. On the other hand, the polyol blend comprises isocyanate reactive components b1, b2 and b3, catalysts (excluding organotin catalyst), pigments, optionally antioxidants and UV absorbers, water absorbers, emulsifiers and, if possible, agents for promoting internal peeling and primers for glass.

An important aspect of the polyol blend is its chemical and physical stability. Chemical stability is obtained by reduced · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

in the amount of "acidic" organo -ismic catalyst, the absence of organotin catalyst and the limited amount of water, which is particularly important in the presence of an organo-lead catalyst. Physical stability is obtained by using mixtures of components b1, b2, b3, C, dispersions of color pigments and possibly emulsifiers, especially when component b2 contains branched glycols such as 2-methyl-1,3-propanediol and 3-methyl- 1,5-pentanediol, and the viscosity of the polyol blends that are sufficiently high at the raw material temperature during storage or manufacture. For example, the viscosity of the polyol blend at 25 ° C is greater than 400 mPas, more preferably greater than 700 mPas, while the viscosity at 45 ° C is greater than 100 mPas, preferably greater than 200 mPas. As mentioned hereinbefore, this viscosity can be increased, for example, by the formation of a quasi-polyol prepolymer of polyether polyols.

Due to the short mold removal time required ("stripping"), the mold of the invention is preheated to a temperature of 60 to 130 ° C, preferably 80 to 120 ° C, and the reaction mixture is injected at a temperature between 30 and 80 ° C, preferably between 40 and 60 ° C.

At these temperatures, the polyol and isocyanate mixtures preferably have a viscosity of 15-2500 mPas, most preferably 200-2000 mPas.

Before closing the mold, a so-called means for supporting the external release of the mold is applied to the mold surface. Especially in the case of window encapsulation applications where the elastomeric molding will be glued to the automobile frame by a separate PU adhesive, according to the invention preferably wax having a melting point or melting point at least equal to, but preferably higher than, the mold temperature, typically 0-30 ° C higher than the mold temperature. This mold temperature is preferably at least 80 ° C and is most preferably between 95 and 110 ° C. In this case the melting point range for the external release agent enhancer forms typically between 110 and • · · · · · · • ·· ·· · · · ······ ··· ··· ··· _N1 ····················

130 [deg.] C. The wax is mainly dispersed in water or an organic solvent.

According to the invention, it has surprisingly been found that by using high mold temperatures (higher than 60 ° C, preferably higher than 80 ° C and most preferably between 95 and 110 ° C) in combination with a mold release agent with a melting point at least equal to the mold temperature , the number of small holes or dots on the surface of the polyurethane elastomer could be kept to a minimum. This is not only important for achieving the optimum visual aspect, such as needed for automotive specifications, but also for obtaining optimal adhesion from the polyurethane elastomer to the molding or the polyurethane adhesive used to fix the window to the car frame.

Furthermore, the minimum amount of small holes or dots is obtained by not using any physical blowing agents and reducing the water content of the isocyanate reactive compound to less than 0.2 wt%, but preferably less than 0.1 wt%, with the amount of water in the total reaction mixture. % is less than 0.15% by weight, but is preferably less than 0.1% by weight.

By adding water absorbing agents (such as zeolites) to the polyol blend, the free water content can be further reduced to practically approach zero. In this case, the risk of small holes or dots is also reduced, even at a lower for my temperature range, eg at 6 0-80 ⁰ C.

According to the invention, it has been found that by the above detailed choice of process conditions and components of the reaction mixture, the R1M process is obtained which is surprisingly well suited for window encapsulation applications, despite the severe conditions the elastomers produced must withstand and the specific characteristics of the elastomers. must show, inter alia, softness, adhesion, · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

XX ·· ·· ·· · ··· · Mechanical strength, etc. Some of these aspects are summarized later in this document.

Adhesion of PU elastomer to glass embossing or PU adhesive

In the case of window encapsulation applications, good adhesion between the PU elastomer and:

on the one hand, the local surface of the glass pane against which the PU elastomer is injected into the mold; and on the other hand, at a later stage, a PU adhesive which serves to bond the PU elastomer to the vehicle frame.

In the method or process of the invention described above, optimal adhesion can be obtained by the following combination:

1) specific selection of the various components of the polyurethane reaction mixture;

2) the use of a mold release agent having a melting point greater than or equal to the mold temperature, so that no film of this molten composition is difficult to remove and forms a physicochemical barrier to the interaction between the PU elastomer surface and the glass or base PU adhesive coatings;

3) the minimum number of small holes or dots as explained above;

4) the use of appropriate primers for cleaners (adhesion promoters). A typical example of such primer coatings applied to a glass surface is a mixture of reactive silanes, a solvent known per se, such as ethyl acetate, and optionally PU prepolymers having an excess of NCO groups, and solvents; and • · · · ··

5) sufficiently high ²³ mechanical ·· · • · • ·

PU elastomer strength, inter alia tensile strength and tear strength, for sufficiently high peel strength during adhesion tests, achieved in particular by the specific choice of the various components of the reaction mixture.

Light and heat stability

The method according to the invention makes it possible to obtain a polyurethane elastomer which can be used in external window encapsulation applications where it must meet the strictest requirements. No significant surface degradation (surface cracks, chalking), discoloration, discoloration or gloss change shall occur, inter alia, in the following weather tests:

Accelerated weather (WOM) tests up to 1000 to 2000 hours, with a xenon lamp or carbon arc lamp and:

a black panel temperature of from 45 to 90 ° C;

continuous or alternating lighting (by rain, eg according to test standard ASTM G26-83, test standard General Motors 00-002 / SAE J 1 960, etc.

long-term, practical field tests with direct weathering for more than one year, including in Florida and Arizona.

this activity or performance can be achieved, inter alia, by combining the following elements in PUelastomeric formulations:

1) accurate, specific isocyanate component choices, containing mainly at least 20% of the IPDI trimer in the IPDI trimer / monomer mixture and having an average functionality of at least 2.2;

2) the type and concentration of antioxidants / absorbers described t

UV radiation;

• ·

3) amino

Initiators having a functionality of at least 2; and

4) type and concentration of color pigments.

Combination of required softness and mechanical strength

The PU elastomers produced by the process of the present invention must generally have a flexural modulus (flexural modulus) according to ASTM D790 in the range of 5 to 300 MPa, but particularly in the range of 10 to 120 MPa, and most typically in the range of 10 to 70 MPa.

However, mechanical strength properties, inter alia tensile strength and tear strength, are reduced in the case of:

a softer material, i.e. in the case of a lower concentration of extenders and / or a lower NCO index; increased percent trimer in the IPDI blend.

According to the present invention, it has been found that sufficient softness of the PU material on the one hand and sufficient mechanical tensile strength, sufficient light and heat stability and a sufficiently short mold removal or "stripping" (fast cure) time on the other side could surprisingly be brought into line although IPDI is used, using the specific compositions of the invention, inter alia:

1) of a polyol type, i.e. a polyetherpolyol having an average nominal functionality of from 2 to 4 and an average equivalent weight of from 800 to 4000, preferably from 1000 to 2000, wherein the polyether polyol is either further likely to have a low monool content, preferably in combination with a primary OH group content of more than 40%, or is prepolymerized to form a quasi-polyol prepolymer with OH-terminated groups, in which case said polyether polyol has a primary polymer content »

OH groups of from 0 to 90%, preferably at least 40%, or has

4445 4 «• 4 · • 4

4 otherwise, • 4

4 • 444 · 4

4,444 444444

in the case of unmodified conventional polyether polyols, a primary OH group content of at least 70%;

2) IPDI trimeric / monomer mixtures containing 20 to 70% by weight of trimmer (average functionality 2.2-2.7) and having an NCO index of between 90 and 120, preferably between 95 and 110;

3) type and concentration of OH-extenders containing two OH groups; and

4) type and concentration of amine initiators.

Absorption and corrugation

If the absorption is too high, eg when the PU encapsulated window is immersed in water (especially cold water), local dimensional deformation ("wrinkling") may occur in the PU elastomer after some time, especially for soft PU elastomer types and / or or smaller PU profile thicknesses and / or longer edges or edges of PU profiles.

According to the present invention, it has been found that the extent of this phenomenon can be reduced:

1) a minimum number of small holes or dots (micropores) on the surface of the PU elastomer; and

2) sufficient physicochemical and chemical crosslinking of the PU elastomer by specifically selected formulations or compositions, inter alia.

type, functionality (f) and polyether polyol concentration (bl) (real functionality> 2 and% EO <30%, preferably <20%, preferably <10% in sum of PO and EO), extenders or extenders (b2) amine initiators (b3) (f> 2), and use of an IPDI trimer such that the functionality of the isocyanate component is at least greater than 2.2;

················································ · To ···· · to ·· «· this · ·· · <

The NCO index, which is likely to be higher or basic polyols s, is preferably greater than 95 and equal to 100, in the case of a conventional relatively high monool content, and

EO.

According to the invention, water absorption can be reduced to less than 10 wt%, and in the case of an EO content of <10%, even less than 3 wt%, calculated on water absorption after immersion of a PU sample having a thickness of about 3 mm into water at 2 ° C for 72 hours.

The process of the present invention is further illustrated below by reference to some specific examples.

DETAILED DESCRIPTION OF THE INVENTION

I. Preparation conditions of fused RIM test plates

The polyol blend (side A) and the isocyanate blend (side B) are mixed in a two-component high pressure mixer head FPL10 (CANNON) attached to the mold and then injected into a die cast aluminum test mold of 1000x200x3 mm in total power or yield. 200 g / sec.

Raw material temperature A and B: 45 ° C Mold temperature: varies (standard: 105 ° C)

Prior to injection, an external peeling agent (ERA) of a given type of wax dispersed in water is sprayed onto the mold surface.

To test the adhesion of RIM pieces to glass (window encapsulation), glass inserts (inserts) are inserted into a specific test form. These glass inserts are then encapsulated in their original place using an injection molded PU-RIM system.

• · · · · · · φφφ · ·φ·· ···φ φφφφφ · · · · · · · φφφφφφφφφφφφφφφφφ φφφφφφφφφφφ φφφφφφ

The various components in the RIM formulations are divided as follows:

side A (polyol mixture):

* H active components (polyols / extenders / crosslinkers) * Catalysts, Catalyst 1 or Catalyst 2 or Catalyst 4 * Components of some antioxidants / UV absorbers (AO / UV) * Color pigment dispersions means to promote internal mold release, emulsifiers, antifoams, water cleaners (eg zeolites).

J side B (even with an o t anate mixture):

* isocyanate (IPDI monomer / isocyanurate mixtures) * catalyst type 3 (tin catalyst) * some AO / UV components typical viscosity of sides A and B at 45 ° C (mPas).

Page A Examples no. 1-8 and 17 9-1 1 12 13/15/16 14 Viscosity at 45 ° C 250 300 1700 150 550 Page B Examples no. 1/2/3/5/6 9-17 4 7 8 Viscosity at 45 ° C 300 150 5 4000

II. Raw materials used in the examples: abbreviations Polyol A

Polyethertriol, made by polyaddition of alkylene oxides (PO and EO) on a glycerine starter, with KOH as a catalyst.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

2o ·· ·· ·· · ·· ··

MW 4800 / number (number) IOH 35 / nominal functionality: 3/85% primary OH groups / 15% EO / viscosity at 25 ° C: 800 mPas

Polyol B

Polyether diol, made by PO polyaddition on glycol starter, with a special double metal cyanide (DMC) catalyst, resulting in less monool / unsaturated by-products compared to conventional KOH catalysis.

brand name: ACCLAIM 2200 (ARCO CHEMICAL C °)

MW 2000 / IOH number 56 / functionality. 2 zero number of primary OH groups (100% secondary OH groups) zero EO content (100% PO) unsaturated compound (monooly): 0.005 meq / g Polyol C

Polyethertriol, made by polyaddition of PO to glycerine starter, with j DMC catalyst Trade name: ACCLAIM 6300 (ARCO CHEMICAL C °)

MW 6000 / IOH number 28 / functionality: 3 zero number of primary OH groups (100% secondary OH groups) zero EO content (100% PO) viscosity at 20 ° C. 1900 mPas (600 mPas at 40 ° C) unsaturated compounds (monooly): 0.015 meq (g

Polyols B-QPP and C-QPP

Quasi-prepolymers measure OH-terminated polyols prepared by reacting a stoichiometric excess of polyol B and polyol C with a certain amount of IPDI monomer, resulting in an expanded polyol with increased viscosity and reduced IOH number.

• · · · · · · · · · · · · · · · · · · · ·

Synthesis of polyols

B-QPP and C-QPP

The base polyol B or C is premixed with lead octoate (catalyst 1) at room temperature. IPD1 is then added with stirring. Final equilibrium viscosity and IOH counts are reached after a maximum of 24 hours.

Ingredients (parts by weight) Viscosity at at equilibrium (in P and s) Number (number) IOH at equilibrium (measured) Basic polyol IPDI Catalyst 1 at 25 ° C at 45 ° C Polyol B-QPP 100 ALIGN! 2.50 0.1 1000 250 44 Polyol C-QPP 100 ALIGN! 1.15 0.2 5000 1700 22nd

Polyol D

Polyether diol, made by polyaddition of PO and EO on a glycol starter, with a special double metal cyanide (DMC) catalyst, resulting in less monool / unsaturated by-products as compared to conventional KOH catalysis.

MW: 2000 / number (number) IOH 56 / functionality 2 / EW: 1000 5 5% primary OH groups / 9% EO

- viscosity at 25 ° C: 430 mPas

- unsaturated compounds (monooles): 0.005 meq / g

Polyol E

Polyethertriol, made by polyaddition of PO to glycerine starter, with conventional KOH catalysis.

- MW: 4000 / number of IOH 42 / rated functionality 3 / EW: 1330 ····················· · · · ························

J (j · * Μ · · · ···· zero number of primary OH groups (100% secondary OH? Groups and 0% EO (100% PO)

- viscosity at 25 ° C: 700 mPas

ISO A and ISO B and ISO C

On-site mixture of IPDI monomer and isocyanurate trimer prepared by trimerization of the IPDI monomer in place at high temperature in the presence of a trimerization catalyst, and further diluting the reaction mixture with IPDI monomer to the desired final NCO content.

NCO content (%) Average functionality C) IPDI weight ratio monomer / trimmer () Viscosity (mPas) at 25 ° C at 45 ° C ISO A 28 2.52 48/52 1000 300 ISO B 32 2,3 1 69/3 1 400 1 50 ISO C 24 2.73 27/73 1 6000 4000

(*) calculated assuming theoretical functionality 3 for the pure IPDI trimmer and an NCO content of 18.9%.

ISO D pure IPDI (isophorone diisocyanate) functionality: 2 / NCO content: 37,8% / viscosity at 20 ° C: 15 mPas EG monoethylene glycol (extender or extender) functionality: 2 / equivalent weight: 31

MP diol

2-Meters 1 - 1, 3Popandi o 1 (Extension) Functionality: 2 / Equivalent Weight: 45

DEOA diethanolamine (crosslinker / "amine initiator") functionality: 3 / equivalent weight: 35.

MEOA ftftftft ftft ftft • · · · • · · · · · · · • · ···· · · · · · · • · ft ······ · · · · · · _{η a} «·· ··· * ··

5} monoethanolamine (extender / "amine initiator") functionality: 2 / equivalent weight: 30

Catalyst 1

Lead 2-ethylhexoate ("lead octoate") - Pb (II) carboxylate containing 33% lead by weight.

Note: A given concentration of Catalyst 1 in the blend examples thus contains part of the Catalyst 1 used to prepare the modified QPP polyols in Examples 9-12.

Catalyst 2

Bismuth 2-ethylhexoate ("Bismuth octoate") = Bi (III) carboxylate containing 24 wt% bismuth and less than 5% free acid.

Catalyst 3

Dimethyltin tin dinodecanoate (Sn (IV) carboxylate)

Catalyst 4

Phenol salt 1.8 diazobicyclo [5.4.0] undecen-7. j

AO / UV mixture consisting of:

- 0.5 parts of triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, which are added to side A (polyol blends)

- 0.5 parts of 2 (2-hydroxy-3,5-di-1-t-amylphenyl) -2H-b e z z 0 ί r and z 1 1, which are added to side A

- 0.5 parts of bis (1,2,2,6,6-pentamethylethyl-4-piperidinyl) sabbaths added to side B (isocyanate mixtures)

- 4.5 parts of tri s (nonylphenyl) phosphite added to side B

Color pigments

- black = soot

- white = titanium dioxide (rutile type)

Baylith (Bayer):

• «· · · · · · · · ·

Water absorbing zeolite paste containing 50% dehydrated sodium potassium aluminosilicate.

Note on the weight ratios of the various components in the examples

All formulations (composition of mixtures) are expressed in parts by weight relative to 100 parts of the active, i.e., isocyanate, reactive components (polyols + extenders + crosslinkers).

In all cases, the pigments were previously dispersed in polyol A, respectively. 20% solids for black and 50% solids for white.

Of these dispersions, 5 parts were added to the corresponding formulations;

- black: 1 part solids + 4 parts polyol A

- white. 2.5 parts solids + 2.5 parts polyol A

The polyol A present in these color dispersions is contained in the total level of polyol A as given in these formulations.

ERA 1 and ERA 2 (means for promoting external peeling) waxes pre-dispersed in organic solvents (hydrocarbons / propanol) Typical wax melting point: for ERA 1: approx. 120 ° C + for ERA 2: approx. 90 ° C typical solid wax content in ERA dispersions: 1-2% lil Reactivity data and physical properties given in the examples:

shortcuts

1) Reactivity data

FT: fiber forming time (in seconds): shows the beginning of gelation (gelation time), ie the moment when the respective gelation time is reached. · · · · · · · · · · · · · · · · · · · · · · · · · ·

Ί} ······· · ·

The fiber may be withdrawn from the reaction mixture by means of a glass rod.

DT mold removal time ("formwork"), ie the cure time in the mold allowing sufficient rigidity of the molding to remove the RIM piece, ie without surface tack, deformation or tearing or pulping when mold removal (formwork).

2) Properties (sample thickness: 3 mm)

D: density of molded PU elastomers in g / l (= kg / m ³ )

Emod: flexural modulus (in MPa) according to ASTM D790.1B

Shore A: surface hardness (in units) according to DIN 53505 test method

ER: ultimate elongation at break (%) according to ASTM D412A Test Method j

RR: tensile strength (in MPa) according to ASTM D412A test method

TR: tear strength (in N / cm) according to ASTM D624C Test Method

WA: water absorption in% by weight of water absorbed, after immersion of the RIM sample in water at 2 ° C for 72 hours. WOM: Weather test (accelerated light and heat / humidity test) under the following test conditions according to ASTM G26 / 1

- ATLAS CI34 with xenon arc

- permanent lighting

- an emissivity of 0,55 W / m ² at 340 nm

- temperature of the crisp panel: 6 3 ⁰ No to ··· ··· · · · · · ··· ··· ················ ··· »··· ··· ······· · ·

cycle: 102 minutes dry / 18 minutes water spray

- filters: outer: quartz / inner: borosilicate

- trial period: 1500 hours

Following the WOM test, the following criteria were evaluated:

- DE: color change (measured by colorimeter)

- gloss retention (%), where initial sample gloss is approximately 75 for high gloss test form% retention of original gloss is given after polishing the sample surface after the aging test

- degradation: visual code:

: no surface degradation, even under the microscope (magnification: 50x): tendency to surface cracks under the microscope: slight surface cracks under the microscope: slight cracks under the microscope (still invisible without microscope)

4/5: some tendency or slight to slight superficial cracks, visible without microscope Adhesion to glass (in the case of window encapsulation applications) (a) sample preparation:

typical automotive glass parts (inserts) are cleaned with heptane and then further processed with:

* BETAW1PE cleaner V P 04 6 0 4-G U R I T ESSEX. wiping and wiping with a cloth (solution of reactive silane in isopropanol) * primer: BETAPRIME 5001-GURIT ESSEX: coating with a solution of isocyanate prepolymers and non-reactive silanes in methyl ethyl ketone) · · · · · · · · ··· »··· ···· ·· · * · ······ ··· · · ·

O r ·········

Jj ·· ·· ·· · ···· Glass and primer curing within 2 hours at 50% RH / 23 ° C The thus prepared glass parts are placed in a special test form, after which the RM system of the glass plate encapsulated is injected under high pressure with RIM are then stored for 7 days under ambient conditions (23 ° C / 50% RH) before testing glass adhesion to the RIM surface by peeling measurement.

b) peel tests (= "glass adhesion") measurement of the adhesion strength in N / cm between glass (primer) and RIM surface by 90 ° peeling, according to DIN-EN 1464

If a tear occurs between the glass / primer and the RIM partition -> surface separation (AF) j

If the core of the RIM sample itself is ruptured -> cohesive failure (CF).

tests are performed on encapsulated glass samples:

* at the initial stage, ie without additional aging * after the cyclic aging test.

immersion in water at 23 ° C for 7 days

- aging of wet samples (packed in aluminum foil) in an oven at 70 ° C for 7 days (100% relative humidity)

- Place these samples in the refrigerator at -23 ° C within 16 hours. · · · ··· · · · ··· ··· ··· ··· ·

3o ·· · * ·· * ··

- reintroduction to ambient conditions within 16 hours (23 ° C / 50% RH) prior to peeling tests.

Adhesion to PU adhesive (in the case of given window encapsulation applications, where the encapsulated window is glued to the car frame by applying the PU adhesive to the RIM surface of the encapsulated window)

a) Sample preparation The surface of the pressed RIM sample is cleaned with heptane the surface is treated with a BETAWIPE 4000 cleaner (GURIT ES SEX) by painting (polyisocyanate in ethyl acetate solution)

- 5 minutes later BETASEAL HV3 (GURIT ESSEX) is applied to the treated RIM surface. HV3 is a highly viscous one-component PU adhesive based on aromatic polyisocyanates containing 0.7% free NCO complex glued RIM / HV3 sample is stored under ambient conditions for 7 days, allowing complete curing of the HV3 (PU) adhesive.

b) peel tests (adhesion of PU adhesive) to evaluate adhesion (visually) between HV3 adhesive and RIM surface according to manual 180 ° peel test * on initial RIM / HV3 samples * on 70 ° C / 100% aging RIM / HV3 samples relative humidity / 7 days and return to ambient conditions (23 ° C / 50% relative humidity) OK criterion = cohesive failure (CF) in the HV3 core itself>

• · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

J / ··········· criterion is not OK% adhesion failure (AF) between <

RIM / HV3 contact surfaces.

Visual appearance -> metallic gloss (code)

After storing RIM parts for 2 months in the dark, in some cases a “metallic shine” may appear locally, which is especially visible in the case of:

* dark colors * higher content of organolead catalyst (catalyst 1)

Visual code after two months of storage in the production area for typical flexible PU foam * code 0: no metallic gloss code 1: slight tendency: almost invisible code 2: slight to slight gloss (visible)

IV. Comment / Interpretation of Results in Examples Examples of series IA to II

Soft, light-stable RIM elastomers were obtained according to the invention with excellent reactivity characteristics and properties f except the following notes in the case of:

Comparative Example 1E (mold temperature <60 ° C):

many micropores on the RIM surface / boundary in terms of

adheze PU adhesives and acceptable mold removal time Example C. 1 F: poor adhesion PU glue due too the low melting point used by ERA relative to mold temperature Example C. 1 G: slight metallic shiny appearance on RIM surface (1 part cat. 1) Example C. 1C: higher water absorption due to lower water absorption NCO 90 in combination with polyol A. Example series 2 to 8

Light-stable RIM elastomers of varying softness were obtained with excellent reactivity characteristics and properties except Comparative Examples 7 and 8.

Example 7 (pure IPDI monomer / trimer) · · · · · · · · · · · · · ·· DI

JO ·· · «·· · ·· ·· -> too long demold time / lower reactivity various small holes or dots on RIM surface -> low stiffness and tensile strength through the use of a higher concentration of extender and NCO index -> mild metal gloss (1 part of catalyst 1 used to increase reactivity)

-> poor WOM resistance (gloss retention / degradation)

-> high enough water absorption

Example 8 (Trimer content too high in IPDI mixture)

-> too reactive (too viscous isocyanate mixture, resulting in poor mixing and flow into the mold, resulting in surface defects such as pinholes or dots etc ...

-> more brittle elastomer compared to other representative examples with similar stiffness.

Note: Replacing the EG extender (MP) with a diol extender in Example 3 greatly improved the physical stability of the polyol blend (side A): no visual settling (decanting) after storage for 7 days at room temperature.

Examples of series 9 to 17

Light-stable RIM elastomers of varying softness with good to excellent reactivity and properties were obtained.

Although polyether ethers without QPP modification and / or with a conventional KOH catalyst (Examples 13-17) were used, good results were still obtained. In these examples, the level of amine initiator or catalyst was increased to compensate for some loss of reactivity compared to the use of QPP-modified polyols or DMC-based polyols with a low monool content. • • · · · · · • • • • • · · · • • • · · • • · · · · · ·

QQ ······· · ·

J7 ·· ·· ·· · ·· ··

Note the excellent reactivity characteristics in Examples 15 and 16 based on DMC catalyzed diol (without QPP modification) containing 55% primary OH groups and limited EO content (9%). In this case, the water absorption values are still good to excellent (even at the NCO 95 index), although they are somewhat higher compared to the use of zero EO-free polyols. E.g. the water absorption in Example 10 is still very low despite the use of a low NCO index of 90. This is due to the use of hydrophobic, completely PO-based polyols.

These examples also showed excellent results in practical corrugation tests: no deformation of the RIM surface after inserting glass encapsulated RIM samples in cold water at 20 ° C for 72 hours.

··· · ·· · · ·

TABLE 1/1: Series IA to II: composition of mixtures

> —1 Axis ^{1 1 1 1} 00 oo o θ 1 1 o ΙΧΊ ^1—1 t ~~ - 1 i what o θ'O ·· ·· Cl - <1 <N § cl 1G / H S2 ' ^{1 1} > 00 - O m ^{1 1} o \ o ι · θ ^{1 1 1} , ‘G, O ΓΊ i O —i I— < Ph O <1 ' ¹ 00 oo o in ¹ 'O (Ti r - i 'i cn 'Ί. ao _o ~ o m SO * - '«« About CS IE (comp.) crC ' ¹ ''oo oo o incl ^{1 1} O l / Ί r- <~ » WHAT Λ, S “T o _o ~ o VO 1. O ΓΊ Q r— O? ' ¹ ' ¹ 00 oo o \ O ^{1 1} O ΙΖΊ 1 - 1 m • Λ, £ O ₀ -O Ό hH 1, g ΓΊ O o < ¹ '''oo ° τ o \ cø ¹ o ΙΧΊ H i - l what %, s -u _o -o bunch \ o · 1 o PQ σ ¹ '' ¹⁰⁰ OO O \ cT ^{1 1} o LTl ' VT) r- i - i cn Λ, S o θ o _ ΚΊ>£><O ι r ¹ O - ΓΊ < ι / Ίo < ¹ ' ^{1 1} 00 ° T o Έ ¹ O O vn U- i - » CQ S, S Έ. o θ o ITi \ O & i> - Example # Polyol A Polyol B Polyol C Polyol B-QPP Polyol C-QPP ISO A ISO B ISO C or D NCO index EG MOdiol DE0A MEO A Catalyst 1 Cat 2 Cat 3 Cat 4 A0 / UV mix Pigment (solid) - black - white Baylith L Mold temperature (° C) Type ERA

• · · · · · · · · · · · · · · · · · · · · · · · ···

TABLE 1/2: Example series IA to II: reactivity and properties

1— < 3 40 | 3 with § - § O 00 80 (AF) 80 (CF) CF - « O o 1G / H 3 40 7 ° C ° M L O> r> Cb £ ~ 1.4 / 1.7 85/90 0/0 80 (AF) 70 (CF) CF > 4 θ O 75 U-t CD ° θ 0 O 2 M S A o -r M D - ° ~ $ o 80 (AF) 70 (CF) % O o 1E (comp.) § o £ £ § £ § O 70 (AF) 60 (CF) CF / AF NOT OK 0-1 Q  £ sssgsg- 2. O _Γ oo 80 (AF) 75 (CF) CF limit 0-1 O m ° o ~ io § θθ 2 t ~~ 2 ~ ⁰⁰ 8 3 O o ^ 00 60 (AF) 55 (CF) CF O o OQ ΓΛ ° $ 0 OO 2 <2 2 Ό, O Tt oo 2 - Tt ⁱⁿ o gs > n tn 00 CF Okay 0 <d ΓΏ ° θ 0 oo 2 <N rR O Tt OO 2 Tt ^fr í O oo \ ........... '1 85 (AF) 75 (CF) CF Tt i O o Example # FT (sec) DT (sec) D (gr / 1) Emod (MPa) Shore A ER Hardness (%) RR (MPa) TR (N / cm) WA (%) x: O O IN) 1 OF O OF -DE - Gloss retention (%) 1 Glass adhesion (N / cm) I 1 Adhesion to PU adhesive Visual appearance RIM surface - small holes or dots - metallic gloss (code)

• · 4 4 • · · · · · · · ·

TABLE 2/1: Example series 1 to 8: composition of mixtures

8 (comp.) 1 / Ί θ '' I ' ¹ Ol C: 61.0 100 ALIGN! 50 '~ ¹ cn V, S O o ⁰ 50 1 o r — M 7 (comp.) r-ι ι i * 00 D: 52.0 | 105 <r> 05 '- » h, s A - o ⁰ tn 50 1 o i £> £ '' ' T. ° CC ¹ 'o 10 - \ O · 50 1 , 'Μ O' un 50 - 1 O r- iri O? »'' ' oo OO O ιθ ^{1 1} o uc - r- i - i m izg m 1 η * ι 1 o o QO 50 1 O XT σι σι ^{1 1 1 1} oo Ol ° ¹ Oi ¹ ° p ~ - t. r — h r— ( S, with T o o ° «Ζ5 50 «O r— rr tzů i i i oo QC o rc '' O in - «05 WHAT o θ o 5T) 50 - 1 o - CU «Ζτ Iii-T 'iii 00 cn About ’ r- O \ '-' WHAT o θ o ΙΧΊ 50 - «θ’— Example # d d d d cxcx <ffl U CQ Ó o * o o o o Jp i- * l o o o o d d d d d ISO A ISO B ISO C or D NCO index EG M0 diol DE0A ΜΕ0Α · - · <N m Tt 4- »4-» d cd d d AO / UV mixture Pigment (solid) - black - White Mold temperature (° C) TypERA

99 9 • 9 9

9 9 9 9 9 · 9 9 9 9 «<. 9 9 9 9

9 9 9 9 9

99 99 99 99

TABLE 2/2: Example series 2 to 8: reactivity and properties

8 (comp.) 3 o o m o cn m o (g o r - σ \ σ \ - / q 5S o 83 (AF) 75 (CF) 1 43 - NOT OK 0-1 7 (comp.) 8 > 120 55 (AF) 49 (CF) CF NOT OK 1-2 AND O 80 (AF) 72 (CF) CF Okay 0 in 2-3 35 § Ό V) 2 “I θ> o o m oo Fj 2 > n o 70 (AF) 60 (CF) CF Okay 0 xr £ | 2 “With £ § C- 2 N C O _ sO 60 (AF) 52 (CF) CF O o Γ * Ί £ OΓ- j / S -f O TT M 2 - no O 00 79 (AF) 70 (CF) CF 7 O <=> CM - £ O CO σ. R ^r o o _ CU 115 (AF) 105 CF CF sd - ΓΖ7 l O o Example # FT (sec) DT (sec) D (gr / 1) Emod (MPa) Shore A ER Hardness (%) RR (MPa) TR (N / cm) WA (%) 45 O O ir> and O OF -DE - Gloss retention (%) - degradation code li Adheze ke. glass (N / cm) - before aging - after cataplasm Adhesion to PU adhesive Visual appearance RIM surface - small holes or dots - metallic gloss (code)

4 ^ • 99 · 9 • 9

TABLE 3/1: Example series 9 to 17: composition of mixtures

r- WO Tt · '' 'l / θ' 00 00 O oo ¹ '° wo r ~~ · - what 00 WO wo ^ o 'θ' θ ' 99 99 WO O t O - Ό WO Tt 1? 1? K? ¹ oo o,. 00 ^{1 1} O in WO r- i - i what O wo 1 ~ ~ 1 - O WO Ό - · About - wo WO Tt i l · »VO« 00 O,, m OO ^{1 1} O \ wo r- i * i WHAT wo wo wo ¹ 0 'o wo O 1— «1 O - S ^{1 1} · o U ^- 1 1 O O ~ Ό i nO i wo wo wo θ ' ¹ o θ' wo NO - 'O -' WHAT S ' ¹ ·' ¹ O \ O tT>> o \ O- ¹ . Ι Ό i wo wo wo θ ' ¹ oo wo Ό - ΙΟΙ—— · fN WO Tt »« tsf »i oo CO O Tt ^{1 1} θ wo U- i - i what wo wo wo θ ' ¹ o o' wo MO - o - - WO vT · i ι i OO CS O O ^{1 1} O <O - WO U- i - i WHAT wo »I—«. 1 O wo MO - 1 O · O WO Tt »irf i» oo CM A '' θ wo Γ * - i what wo r— 1 O wo MO - i O - Cb WO O i 1 Q-f 1 1 · OO CM O o ^{1 1} θ o - 1— 1 - 1 what wo »- 1 <- 1 O wo MO - 1 O - Example no (X, fX IX (X C / θ ' CfflOfflO Q W o o o o o o o κΟ, ~ o o o o o o P- <Ph pL (Pm pL <P- (Ph ISO A ISO B ISO C or D NCO index EG MO diol DE0A ΜΕ0Α Catalyst 1 Cat 2 Cat 3 Cat 4 A0 / UV mixture Pigment (solid) - black - White Mold temperature (° C) Type ERA

···· ··

TABLE 3/2: Examples 9 to 17: Reactivity and Properties

t <o £ s and § g = § 5 7 ΙΖΊ 7 - r - o 60 (AF) 55 (CF) II X. Okay 1 ! § <* § p T m 7 r - t 0 65 (AF) 55 (CF) CF Okay 0 in 4 30 § ΚΙ θ 'L θ °° - 0 fx) 00 fxj CM 7 o 7 - oo o 55 (AF) 48 (CF) CF 83 7 O o O C * ~> ? o o 2 m 2 7, O 'Λ Ο' Ε - - -1 1 73 (AF) 65 (CF) CF 84 7 O ó 6 40 ° v-, oc 9 n S B O Tt M o - o 68 (AF) 60 (CF) CF 84 ~ O CN M- ° ^ln S θ 7 O n oo ff _ IS ° 72 (AF) 65 (CF) CF 84 ~ μ. i O o 4 40 θ ΙΠ o θ cl θ 7 2 ^M £ - £ - - | 63 (AF) 55 (CF) CF Okay 0 O - 3 >r>C> m 2 ^1/1 2 ⁰⁰ O - in JQ m 2 ' OO _o rj L φ 2 55 (AF) 55 (CF) CF limit OK 1 σ> - £ čn iz> O 2 · - 2 ^{lZ l} O rl oo ° ~ ý „ 65 (AF) 58 (CF) CF 84 _ o Example # FT (sec) DT (sec) D (gr / 1) Emod (MPa) Shore A ER Hardness (%) RR (MPa) TR (N / cm) WA (%) x O O «ΖΊ t with O £ -DE - Gloss retention (%) - degradation code II Glass adhesion (N / cm) - before aging - after cataplasm || Adhesion to PU adhesive Visual appearance RIM surface - tiny holes or dots - metallic gloss (code)

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Claims (24)

PATENT CLAIMS Method for producing microcellular or non-cellular, light-stable elastomeric, flexible or semi-flexible polyurethane moldings having a density of at least 900 kg / m ³ and a bending modulus according to ASTM D790 of between 5 and 300 MPa, and in particular between 10 and 120 MPa injection molding, where: A) an isocyanate component comprising an isophorone diisocyanate (IPDI) trimmer / monomer mixture having an NCO content of from 24.5 to 34% by weight, preferably from 26 to 32% by weight, reacts with (B) isocyanate reactive components, containing: b1) a polyol component comprising a polyether polyol having terminal OH groups, an average nominal functionality of from 2 to 4 and an average equivalent weight of from 800 to 4000, preferably from 1000 to 2000; b2) about 3 to 20 wt%, preferably about 5 to 15 wt%, by weight of the respective components b1, b2 and b3 of at least one chain extender having only aliphatic or alicyclic OH groups as functional groups, functionality 2, equivalent weight up to 80 at most and content of primary OH groups at least 50%, b3) from about 2 to 10 wt%, preferably from about 2.5 to 6 wt%, based on the weights b1, b2 and b3, of at least one amine component an initiator forming a parallel catalyst system with catalyst component C and having 2 to 3 functional aliphatic NH =, NH ₂ - or OH groups, at least one of which is a secondary or primary amino group, and an equivalent weight of up to 150 at most at most; At this moment C) at least one catalyst component selected from the group consisting of organo-lead (II), organovismic (III), and 0 00 _ _ · 0 0 0 0 0 0 0000 0 00 0 Organotin (IV) catalysts, the maximum amount of each of these catalysts being 1.5 wt%, preferably 1 wt%, for an organo-lead catalyst, bismuth catalyst 1.5 wt% and for organotin catalyst 3 wt%, based on the weight of components b1, b2 and b3, wherein the organotin catalyst is used either in combination with an organo-lead and / or organo-mismuth catalyst, and / or in combination with diazobicycloalkene a catalyst and / or a salt of the latter weak acid catalyst; D) at least one pigment component, and E) at least one antioxidant / absorbent component; wherein said components are treated with a two-component solvent-free polyurethane reaction injection molding process at an isocyanate index of from 90 to 120, preferably from 95 to 110, in a preheated form at a temperature of from 60 to 130 ° C, preferably from 80 to 120 ° C, the reaction mixture is injected at a temperature between 30 and 80 ° C, more preferably between 40 and 60 ° C, wherein the polyurethane reaction mixture is substantially free of physical blowing agents and contains up to 0.15 wt%, preferably up to 0.10 wt% % water according to the total weight of the reaction mixture. 2. The process according to claim 1, wherein the polyether polyol component b1 is a propylene oxide addition product and preferably a low molecular weight initiator ethylene oxide, wherein the amount of ethylene oxide, if present, is less than 30% of the total amount of ethylene oxide. and propylene oxide. 3. The method of claim 2 wherein said amount of ethylene oxide is less than about 20% and most preferably less than or equal to about 10%. The process according to claim 2 or 3, wherein said polyether polyol has a primary OH group content of at least 70%. Process according to any one of claims 2 to 4, characterized in that said polyether polyol is pre-polymerized with a part of said isocyanate component to form a quasi-prepolymer of polyols with terminal OH groups. Method according to claim 4 or 5, characterized in that said polyether polyol has an average nominal functionality of 2.5 to 4 and an average equivalent weight of 1000 to 1500. Method according to any one of claims 2 to 6, characterized in that a polyether polyol having a low monool content is used, in particular the equivalent monool content is less than 5%. The method of claim 7, wherein said polyether polyol has a nominal average functionality of from 2 to 3 and an average equivalent weight of from 1,000 to 2000. Process according to any one of claims 5 to 8, characterized in that said polyether polyol has a primary OH group content of at least 40%. Method according to claim 1, characterized in that polytetramethylene glycol (PTMG) is used as the polyether polyol component b1. The method of any one of claims 1 to 10, wherein the IPDI trimer in said IPDI trimmer / monomer mixture is an isophorone isocyanurate trimer. Process according to any one of claims 1 to 11, characterized in that the mold is preheated to a temperature of at least 90 ° C, preferably to a temperature of from 95 to 110 ° C. Method according to any one of claims 1 to 12, characterized in that the agent for promoting external peeling of the molds is applied to the mold prior to injection of the reaction mixture, wherein said composition is at least equal to melting point but preferably higher than the mold temperature. up to 30 ° C higher than the mold temperature. Process according to claim 13, characterized in that a wax dispersed in water or an organic solvent is used as a means to promote external peeling of the molds. Process according to any one of claims 1 to 14, characterized in that an organoleaded and / or organo-bismuth catalyst is used, in particular in combination with 0.2 to 1 wt.%, Based on the weight of the components. b1, b2 and b3, said organotin catalyst and / or in combination with 0.1 to 1 wt%, based on the weight of components b1, b2 and b3, of said diazobicycloalkene catalyst. 16. The method of claim 15, wherein a combination of said said organolead catalyst in a diazobicycloalkene catalyst in an organotin catalyst is used. The process according to any one of claims 1 to 16, wherein the isocyanate component A further comprises up to 10 wt% of a prepolymer, with end isocyanate groups, IPDI isocyanate reactive compounds containing 2 to 4 isocyanate reactive, hydrogen-containing groups , preferably OH groups. The method of any one of claims 1 to 17, wherein said amine initiator is selected from the following different types: I. alkanolamine-type crosslinkers with one secondary NH group and two OH groups, preferably primary OH groups; II. extenders with one primary NH 2 group and one primary OH group located on adjacent carbon atoms; III. extenders (chains) with one secondary NH group and one primary OH group; IV. extenders having two primary NH ₂ groups, at least one of which is attached to the cyclic ring; and V. extenders having two secondary NH groups having a branched alkyl or cycloalkyl group having at least four carbon atoms attached thereto or crosslinking agents having three secondary NH groups, at least two of which have a branched alkyl or cycloalkyl group to which at least four carbon atoms are attached atoms. 19. The process of claim 18 wherein said amine initiator comprises at least about 1% by weight based on &lt; RTI ID = 0.0 &gt; 9 &lt; / RTI &gt; The weight of the components b1, b2 and b3, diethanolamine (DEOA) in combination with an amine initiator of the chain (chain) type, in particular monoethanolamine (MEOA), to achieve an average functionality of between 2 and 3. The method of any one of claims 1 to 19, wherein the antioxidant / UV absorber component comprises; 0.1-1 wt.%, Preferably 0.2-0.6 wt.%, Based on the weight of the reaction mixture, of the substituted phenolic type primary antioxidant; 0.1-1 wt.%, Preferably 0.2-0.6 wt.%, Based on the weight of the reaction mixture, substituted with HICAL (Hindered Aliphatic Light Stabilisers); 0-5 wt.%, Preferably less than 3 wt.%, Based on the weight of the reaction mixture, peroxide decomposers, preferably of the aliphatic or aromatic organophosphite type; and 0.1-1 wt%, preferably 0.2-0.6 wt%, based on the weight of the reaction mixture of the UV absorber, which is preferably of the benzotriazole type. Method according to any one of claims 1 to 20, characterized in that said polyurethane molding is applied as a flexible or flexible flat gasket around the perimeter of the window by placing the window with its perimeter in a mold near the mold and injecting the polyurethane reaction mixture into the closed forms. 22. Microcellular or non-cellular, light-stable elastomeric, flexible or flexible polyurethane molding having a density of at least 900 kg / m ³ and a bending modulus according to ASTM D790 of between 5 and 300 MPa, and in particular between 10 and 120 MPa, more precisely in encapsulating form. a window gasket that can be obtained by a reaction according to a reaction injection molding method (molding); Isocyanate components comprising an isophorone diisocyanate (IPDI) trimer / monomer mixture having an NCO content of from 24.5 to 34% by weight, preferably from 26 to 32% by weight; «·« «« «« «« «« «« «« «« «« «« « (B) isocyanate reactive components, containing: b1) a polyol component comprising a polyether polyol having terminal OH groups, an average nominal functionality of from 2 to 4 and an average equivalent weight of from 800 to 4000, preferably from 1000 to 2000; b2) about 3 to 20 wt%, preferably about 5 to 15 wt%, based on the weight of the respective components b1, b2 and b3, of at least one chain extender having only aliphatic or alicyclic OH groups as functional groups, functionality 2, equivalent weight up to 80 at most and a primary OH content of at least 50%; b3) from about 2 to 10 wt%, preferably from about 2.5 to 6 wt%, based on the weights b1, b2 and b3, of at least one component of the amine initiator forming the catalyst system with component C and having 2 to 3 functional aliphatic NH =, NH ₂ - or OH-groups, at least one of which is a secondary or primary amino group, and an equivalent weight of up to 150 at most, but preferably up to 100 at most; At this moment C) at least one catalyst component selected from the group consisting of organo-lead (II), organo-mismatch (III) and organotin (IV) catalysts, the maximum amount of each of these catalysts being 1.5 wt%, preferably 1 wt. and for organotin catalyst 3 wt.%, based on the weight of components b1, b2 and b3, wherein the organotin catalyst is used either in combination with an organolead and / or organovismuth catalyst, and / or in combination with an organotin catalyst. a diazobicycloalkene catalyst and / or a salt of the latter weak acid catalyst; D) at least one pigment component, and E) at least one antioxidant / UV absorbent component; wherein said components are treated with a two-component solvent-free polyurethane reaction method and an injection molding process at an isocyanate index of from 90 to 120, preferably from 95 to 110, in the form preheated to a temperature of from 60 to 130 ° C, preferably from 80 to 120 ° C, wherein the reaction mixture is injected at a temperature of between 30 and 80 ° C, more preferably between 40 and 60 ° C, wherein the polyurethane reaction mixture is substantially free of physical blowing agents and contains up to 0.15 wt%, preferably up to 0.10 wt% at most, of water based on the total weight of the reaction mixture. Polyurethane molding according to claim 22, characterized in that it has a water absorption of less than 10, preferably less than 3 wt.% Of the water absorption after immersion of a PU sample having a thickness of about 3 mm in water at 2 ° C for 72 hours. A polyol blend and isocyanate blend system for use in a two-component injection molding reaction process comprising the components as set forth in any one of claims 1 to 21.